The present invention relates to antimicrobial detergent compositions for reducing microorganisms on hard surfaces and for cleaning hard surfaces, as well as methods of reducing microorganisms on hard surfaces and cleaning hard surfaces. The present antimicrobial compositions and methods minimize the amount of streaks left on the treated surfaces, even in situations where the compositions are not rinsed from the treated surface.
Hard surface cleaning compositions having antimicrobial effectiveness are known in the art. Such compositions are able to both clean soils from surfaces and reduce microorganisms present on surfaces. However, many of these compositions are not suitable for many hard surfaces, such as ceramic tile, vinyl, linoleum, finished wood floors, laminates, and the like, because the compositions tend to leave significant filming and/or streaking of the surface, resulting in an appearance that is unacceptable to consumers. A number of attempts have been made to address the filming and/or streaking problems associated with these types of compositions.
For example, EP 342,997 B2 granted to Rennie et al. disclose a general-purpose cleaning composition comprising from 0.01 to 90% by weight of a nonionic surfactant, 0.005 to 50% by weight of a cationic surfactant which has a sanitising action, and 0.003 to 20% by weight of a non-anionic polymer which has an adsorptive affinity to hard surfaces. Rennie et al. teach that its compositions usually contain from 0.1 to 30% by weight of nonionic surfactant, and that its compositions should contain at least 1% of nonionic surfactant to obtain both reduced streaking and improved cleaning effects.
Others have developed compositions utilizing cationic polymer and antimicrobial biguanide compounds to provide sanitization of other types of surfaces, such as human skin. For example, U.S. Pat. No. 6,045,817, issued Apr. 4, 2000 to Ananthapadmanabhan et al. discloses an antibacterial cleaning composition containing from about 0.05% to about 1% of a cationic polymer having a charge density of 0.0025 or higher, from about 0.2 to about 5% of a zwitterionic surfactant, from about 0.2% to about 5% of at least one biguanide compound, optionally nonionic surfactant and a polymeric biocide compound, and has a pH of 7.5 or greater. The composition of the ""817 patent is used for handwashing purposes and is said to exhibit improved mildness, while providing antimicrobial effectiveness.
However, antimicrobial hard surface cleaning compositions still lead to filming and/or streaking problems on hard surfaces that are unacceptable to consumers, especially when the compositions are left to dry on the surface without rinsing. As a result, consumers typically rinse such compositions from the treated surfaces with water in order to reduce the residue left by such compositions.
It has thus been desired to develop an antimicrobial, hard surface cleaning composition that is able to effectively clean soils from surfaces, reduce microorganisms on the surface (i.e. disinfect the surface), while leaving the surface essentially free of filming and/or streaking, even when such compositions are left to dry on the surface without rinsing.
The present invention relates to antimicrobial, hard surface cleaning compositions that effectively clean and reduce microorganisms on a surface without resulting in unacceptable filming and/or streaking residue on the surface. The present compositions generally comprise (a) cationic antimicrobial active; (b) nitrogen-containing polymer; and (c) surfactant. Preferred antimicrobial, hard surface cleaning compositions of the present invention for use in no-rinse cleaning methods typically comprise (a) from about 0.001% to about 0.5%, by weight of the composition, of surfactant; (b) cationic antimicrobial active; and (c) nitrogen-containing polymer.
The present invention further relates to methods of cleaning and reducing microorganisms on hard surfaces comprising contacting the surfaces with such compositions and preferably allowing the compositions to dry on the surface without rinsing the composition from the surface using water or other rinsing solution.
The present invention further encompasses kits for cleaning and reducing microorganisms on surfaces comprising a container having therein such compositions and a disposable cleaning pad having a t1200 absorbent capacity of at least about 1 gram of water per gram of cleaning pad.
The present invention encompasses antimicrobial compositions for cleaning and/or disinfecting hard surfaces, especially household surfaces such as ceramic tile, vinyl, linoleum, finished wood floors, laminates, and the like. The antimicrobial compositions of the present invention generally comprise (a) cationic antimicrobial active; (b) nitrogen-containing polymer; and (c) surfactant. The present compositions can further comprise optional ingredients such as aqueous carrier, buffer, perfume, suds suppressor, and the like.
It has been found that incorporating nitrogen-containing polymers, especially certain types of modified polyamine polymers, in hard surface cleaning compositions containing cationic antimicrobial actives serves to substantially eliminate much of the filming and/or streaking residue left on surfaces by such compositions that do not contain nitrogen-containing polymers, especially when such compositions are used in xe2x80x9cno-rinsexe2x80x9d cleaning methods. As used herein, the term xe2x80x9cno-rinsexe2x80x9d refers to cleaning methods wherein the cleaning composition is allowed to dry on the surface being cleaned without rinsing the composition from the surface with water (or other rinsing solutions).
It has further been found that incorporating such nitrogen-containing polymers in hard surface cleaning compositions also significantly helps the wetting and spreading properties of the composition, to allow for better surface coverage and better cleaning and disinfecting performance. Indeed, the preferred compositions herein provide contact angles, as measured according to the Contact Angle Measurement Test Method as described in Section IV infra, of less than about 30xc2x0, preferably less than about 20xc2x0, and more preferably less than about 15xc2x0.
The antimicrobial, hard surface cleaning compositions herein relate to both traditional all-purpose cleaning compositions used in traditional cleaning methods, and also to low-surfactant compositions preferably used in no-rinse cleaning methods. Traditional all-purpose cleaning compositions tend to comprise a wide range of surfactant levels, as well as other components, and can be used neat or can be diluted to form dilute cleaning compositions. Such compositions are typically applied to the surface to be cleaned and then rinsed from the surface with water (or other rinsing solutions).
The preferred antimicrobial, hard surface cleaning compositions herein comprise relatively low levels of surfactant (i.e. levels of surfactant less than about 0.5%, by weight of the composition) and are preferably used in no-rinse cleaning methods. Such compositions can be applied to the surface to be cleaned and then allowed to dry on the surface without rinsing the composition from the surface with water (or other rinsing solutions). Even in such no-rinse cleaning methods, these compositions do not leave unsightly filming and/or streaking on the treated surface. As a result, such compositions are highly acceptable and desirable to consumers, since they are easy to use (e.g. no need for rinsing) and provide an acceptable end cleaning result.
A. CATIONIC ANTIMICROBIAL ACTIVES
The compositions herein comprise cationic antimicrobial actives such that the compositions are capable of reducing or killing microorganisms on surfaces to be treated with the compositions. A variety of cationic antimicrobial actives can be used in the present compositions. However, as mentioned hereinbefore, compositions comprising cationic antimicrobial actives tend to leave unsightly filming and/or streaking on the treated surfaces. As a result, the compositions herein should further comprise a nitrogen-containing polymer, especially a modified polyamine polymer as described infra, to mitigate this effect.
Cationic antimicrobial actives useful herein are preferably selected from the group consisting of C6-C18 alkyltrimethylammonium chlorides, C6-C18 dialkyldimethylammonium chlorides, C6-C18 alkylbenzyldimethylammonium chloride, chlorhexidine diacetate, chlorhexidine dihydrochloride, chlorhexidine digluconate, benzethonium chloride, and mixtures thereof. Particularly preferred cationic antimicrobial actives herein are chlorhexidine, or salts thereof, and dialkyldimethylammonium chlorides.
The preferred compositions herein comprise two or more different cationic antimicrobial actives to provide enhanced antimicrobial efficacy. Preferably, the compositions comprise at least one quaternary cationic antimicrobial active and at least one biguanide antimicrobial active. Such actives are preferably in a ratio of quaternary cationic antimicrobial active to biguanide antimicrobial active of from about 10:1 to about 1:10, and more preferably from about 5:1 to about 1:5, by weight.
In a preferred embodiment, the antimicrobial, hard surface cleaning composition of the present invention comprises a chlorhexidine salt, preferably chlordexidine diacetate, and a dialkyldimethylammonium chloride, preferably didecyldimethylammonium chloride (Bardac(copyright) 2250).
In general, the antimicrobial, hard surface cleaning compositions of the present invention comprise cationic antimicrobial active at a level of from about 0.005% to about 10%, preferably from about 0.005% to about 5%, and more preferably from about 0.005% to about 1%, by weight of the composition.
In preferred low-surfactant compositions for use in no-rinse cleaning methods, such compositions typically comprise cationic antimicrobial active at a level of from about 0.005% to about 1%, preferably from about 0.005% to about 0.5%, and more preferably from about 0.005% to about 0.2%, by weight of the composition.
1. Quaternary Compounds
A wide range of quaternary compounds can also be used as antimicrobial actives, in conjunction with the preferred surfactants. Non-limiting examples of useful quaternary compounds include: (1) benzalkonium chlorides and/or substituted benzalkonium chlorides such as commercially available Barquat(copyright) (available from Lonza), Maquat(copyright) (available from Mason), Variquat(copyright) (available from Witco/Sherex), and Hyamine(copyright) (available from Lonza); (2) di(C6-C14)alkyl di short chain (C1-4 alkyl and/or hydroxyalkl) quaternary such as Bardac(copyright) products of Lonza, (3) N-(3-chloroallyl)hexaminium chlorides such as Dowicide(copyright) and Dowicil(copyright) available from Dow; (4) benzethonium chloride such as Hyamine(copyright) from Rohm and Haas; (5) methylbenzethonium chloride represented by Hyamine(copyright) 10 X supplied by Rohm and Haas, (6) cetylpyridinium chloride such as Cepacol chloride available from of Merrell Labs. Examples of the preferred dialkyl quaternary compounds are di(C8-C12)dialkyl dimethyl ammonium chloride, such as didecyldimethylammonium chloride (Bardac 22), and dioctyldimethylammonium chloride (Bardac 2050). The quaternary compounds useful as cationic antimicrobial actives herein are preferably selected from the group consisting of dialkyldimethylammonium chlorides, alkyldimethylbenzylammonium chlorides, dialkylmethylbenzylammonium chlorides, and mixtures thereof. Other preferred cationic antimicrobial actives useful herein include diisobutylphenoxyethoxyethyl dimethylbenzylammonium chloride (commercially available under the trade name Hyamine(copyright) 1622 from Rohm and Haas) and (methyl)diisobutylphenoxyethoxyethyl dimethylbenzylammonium chloride (i.e. methylbenzethonium chloride). Typical concentrations for biocidal effectiveness of these quaternary compounds, especially in the preferred low-surfactant compositions herein, range from about 0.001% to about 0.8%, preferably from about 0.005% to about 0.3%, more preferably from about 0.005% to about 0.08%, and even more preferably from about 0.005% to about 0.06%, by weight of the usage composition.
The surfactants, as described infra, when added to the present compositions, tend to provide improved antimicrobial action.
2. Biguanides
Other useful cationic antimicrobial actives herein include biguanide compounds, either. alone or in combination with other cationic antimicrobial actives. Especially useful biguanide compounds include 1,1xe2x80x2-hexamethylene bis(5-(p-chlorophenyl)biguanide), commonly known as chlorhexidine, and its salts, e.g., with hydrochloric, acetic and gluconic acids. The digluconate salt is highly water-soluble, about 70% in water, and the diacetate salt has a solubility of about 1.8% in water. When chlorhexidine is used as a cationic antimicrobial active in the present invention it is typically present at a level of from about 0.001% to about 0.4%, preferably from about 0.002% to about 0.1%, and more preferably from about 0.005% to about 0.06%, by weight of the usage composition. In some cases, a level of from about 0.09% to about 1% may be needed for virucidal activity.
Other useful biguanide compounds include Cosmoci(copyright) CQ(copyright), Vantocil(copyright)IB, including poly(hexamethylene biguanide) hydrochloride. Other useful cationic antimicrobial actives include the bis-biguanide alkanes. Usable water soluble salts of the above are chlorides, bromides, sulfates, alkyl sulfonates such as methyl sulfonate and ethyl sulfonate, phenylsulfonates such as p-methylphenyl sulfonates, nitrates, acetates, gluconates, and the like.
Examples of suitable bis biguanide compounds are chlorhexidine; 1,6-bis-(2-ethylhexylbiguanidohexane)dihydrochloride; 1,6-di-(N1,N1xe2x80x2-phenyldiguanido-N5,N5xe2x80x2)-hexane tetrahydrochloride; 1,6-di-(N1,N1xe2x80x2-phenyl-N1,N1xe2x80x2-methyldiguanido-N5,N5xe2x80x2)-hexane dihydrochloride; 1,6-di(N1,N1xe2x80x2-o-chlorophenyldiguanido-N5,N5xe2x80x2)-hexane dihydrochloride; 1,6-di(N1,N1xe2x80x2-2,6-dichlorophenyldiguanido-N5,N5xe2x80x2)hexane dihydrochloride; 1,6-di[N1,N1xe2x80x2-.beta.-(p-methoxyphenyl)diguanido-N5,N5xe2x80x2]-hexane dihydrochloride; 1,6-di(N1,N1xe2x80x2-.alpha.-methyl-.beta.-phenyldiguanido-N5,N5xe2x80x2)-hexane dihydrochloride; 1,6-di(N1,N1xe2x80x2-p-nitrophenyldiguanido-N5,N5xe2x80x2)hexane dihydrochloride; .omega.:.omega.xe2x80x2-di-(N1,N1xe2x80x2-phenyldiguanido-N5,N5xe2x80x2)-di-n-propylether dihydrochloride; .omega:omegaxe2x80x2-di(N1,N1xe2x80x2-p-chlorophenyldiguanido-N5,N5xe2x80x2)-di-n-propylether tetrahydrochloride; 1,6-di(N1,N1xe2x80x2-2,4-dichlorophenyldiguanido-N5,N5xe2x80x2)hexane tetrahydrochloride; 1,6-di(N1,N1xe2x80x2-p-methylphenyldiguanido-N5,N5xe2x80x2)hexane dihydrochloride; 1,6-di(N1,N1xe2x80x2-2,4,5-trichlorophenyldiguanido-N5,N5xe2x80x2)hexane tetrahydrochloride; 1,6-di[N1,N1xe2x80x2.alpha.-(p-chlorophenyl)ethyldiguanido-N5,N5xe2x80x2]hexane dihydrochloride; .omega.:.omega.xe2x80x2di(N1,N1xe2x80x2-p-chlorophenyldiguanido-N5,N5xe2x80x2)m-xylene dihydrochloride; 1,12-di(N1,N1xe2x80x2-p-chlorophenyldiguanido-N5,N5xe2x80x2)dodecane dihydrochloride; 1,10-di(N1,N1xe2x80x2-phenyldiguanido-N5,N5xe2x80x2)-decane tetrahydrochloride; 1,12-di(N1,N1xe2x80x2-phenyldiguanido-N5,N5xe2x80x2) dodecane tetrahydrochloride; 1,6-di(N1,N1xe2x80x2-o-chlorophenyldiguanido-N5,N5xe2x80x2)hexane dihydrochloride; 1,6-di(N1,N1xe2x80x2-p-chlorophenyldiguanido-N5,N5xe2x80x2)-hexane tetrahydrochloride; ethylene bis(1-tolyl biguanide); ethylene bis(p-tolyl biguanide); ethylene bis(3,5-dimethylphenyl biguanide); ethylene bis(p-tert-amylphenyl biguanide); ethylene bis(nonylphenyl biguanide); ethylene bis(phenyl biguanide); ethylene bis(N-butylphenyl biguanide); ethylene bis(2,5-diethoxyphenyl biguanide); ethylene bis(2,4-dimethylphenyl biguanide); ethylene bis(o-diphenylbiguanide); ethylene bis(mixed amyl naphthyl biguanide); N-butyl ethylene bis(phenylbiguanide); trimethylene bis(o-tolyl biguanide); N-butyl trimethylene bis(phenyl biguanide); and the corresponding pharmaceutically acceptable salts of all of the above such as the acetates; gluconates; hydrochlorides; hydrobromides; citrates; bisulfites; fluorides; polymaleates; N-coconutalkylsarcosinates; phosphites; hypophosphites; perfluorooctanoates; silicates; sorbates; salicylates; maleates; tartrates; fumarates; ethylenediaminetetraacetates; iminodiacetates; cinnamates; thiocyanates; arginates; pyromellitates; tetracarboxybutyrates; benzoates; glutarates; monofluorophosphates; and perfluoropropionates, and mixtures thereof. Preferred antimicrobials from this group are 1,6-di-(N1,N1xe2x80x2-phenyldiguanido-N5,N5xe2x80x2)-hexane tetrahydrochloride; 1,6-di(N1,N1xe2x80x2-o-chlorophenyldiguanido-N5,N5xe2x80x2)-hexane dihydrochloride; 1,6-di(N1,N1xe2x80x2-2,6-dichlorophenyldiguanido-N5,N5xe2x80x2)hexane dihydrochloride; 1,6-di(N1,N1xe2x80x2-2,4-dichlorophenyldiguanido-N5,N5xe2x80x2)hexane tetrahydrochloride; 1,6-di[N1,N1xe2x80x2-.alpha.-(p-chlorophenyl)ethyldiguanido-N5,N5xe2x80x2]hexane dihydrochloride; .omega.:.omega.xe2x80x2di(N1,N1xe2x80x2-p-chlorophenyldiguanido-N5,N5xe2x80x2)m-xylene dihydrochloride; 1,12-di(N1,N1xe2x80x2-p-chlorophenyldiguanido-N5,N5xe2x80x2)dodecane dihydrochloride; 1,6-di(N1,N1xe2x80x2-o-chlorophenyldiguanido-N5,N5xe2x80x2)hexane dihydrochloride; 1,6-di(N1,N1xe2x80x2-p-chlorophenyldiguanido-N5,N5xe2x80x2)-hexane tetrahydrochloride; and mixtures thereof; more preferably, 1,6-di(N1,N1xe2x80x2-o-chlorophenyldiguanido-N5,N5xe2x80x2)-hexane dihydrochloride; 1,6-di(N1,N1xe2x80x2-2,6-dichlorophenyldiguanido-N5,N5xe2x80x2)hexane dihydrochloride; 1,6-di(N1,N1xe2x80x2-2,4-dichlorophenyldiguanido-N5,N5xe2x80x2)hexane tetrahydrochloride; 1,6-di[N1,N1xe2x80x2-.alpha.-(p-chlorophenyl)ethyldiguanido-N5,N5xe2x80x2]hexane dihydrochloride; .omega.:.omega.xe2x80x2di(N1,N1xe2x80x2-p-chlorophenyldiguanido-N5,N5xe2x80x2)m-xylene dihydrochloride; 1,12-di(N1,N1xe2x80x2-p-chlorophenyldiguanido-N5,N5xe2x80x2)dodecane dihydrochloride; 1,6-di(N1,N1xe2x80x2-o-chlorophenyldiguanido-N5,N5xe2x80x2)hexane dihydrochloride; 1,6-di(N1,N1xe2x80x2-p-chlorophenyldiguanido-N5,N5xe2x80x2)-hexane tetrahydrochloride; and mixtures thereof. As stated hereinbefore, the bis biguanide of choice is chlorhexidine and its salts, e.g., digluconate, dihydrochloride, diacetate, and mixtures thereof.
B. NITROGEN-CONTAINING POLYMERS
It has been surprisingly found that certain polymers, e.g. nitrogen-containing polymers, tend to mitigate the unwanted filming and/or streaking associated with compositions for cleaning hard surfaces that contain cationic antimicrobial actives, especially quaternary and/or biguanide antimicrobial actives.
Nitrogen-containing polymers useful herein include polymers that contain amines (primary, secondary, and tertiary), amine-N-oxide, amides, urethanes, and/or quaternary ammonium groups. It is important that the polymers herein contain nitrogen-containing groups that tend to strongly interact with the surface being treated in order to displace the cationic antimicrobial actives from the surface.
Preferably, the polymers herein contain basic nitrogen groups. Basic nitrogen groups include primary, secondary, and tertiary amines capable of acting as proton acceptors. Thus the preferred polymers herein can be nonionic or cationic, depending upon the pH of the solution. Polymers useful herein can include other functional groups, in addition to nitrogen groups. The preferred polymers herein are also essentially free of, or free of, quaternary ammonium groups.
Preferably, the polymers herein are branched polymers, especially highly branched polymers including comb, graft, starburst, and dendritic structures. Preferably, the polymers herein are not linear polymers.
The nitrogen-containing polymers herein can be an unmodified or modified polyamine, especially an unmodified or modified polyalkyleneimine. Preferably, the nitrogen containing polymers herein are modified polyamines. Poly(C2-C12 alkyleneimines) include simple polyethyleneimines and polypropyleneimines as well as more complex polymers containing these polyamines. Polyethyleneimines are common commercial materials produced by polymerization of aziridine or reaction of (di)amines with alkylenedichlorides. Polypropyleneimines are also included herein.
Although modified polyamines are preferred, linear or branched polyalkyleneimines, especially polyethyleneimines or polypropyleneimines, can be suitable in the present compositions to mitigate filming and/or streaking resulting from such compositions containing cationic antimicrobial actives. Branched polyalkyleneimines are preferred to linear polyalkyleneimines. Suitable polyalkyleneimines typically have a molecular weight of from about 1,000 to about 30,000 Daltons, and preferably from about 4,000 to about 25,000 Daltons. Such polyalkyleneimines are free of any ethoxylated and/or propoxylated groups, as it has been found that ethoxylation or propoxylation of polyalkyleneimines reduces or eliminates their ability to mitigate the filming and/or streaking problems caused by compositions containing cationic antimicrobial actives.
In general, the antimicrobial, hard surface cleaning compositions of the present invention comprise nitrogen-containing polymer at a level of from about 0.005% to about 10%, preferably from about 0.005% to about 5%, and more preferably from about 0.005% to about 1%, by weight of the composition.
In preferred low-surfactant compositions for use in no-rinse cleaning methods, such compositions typically comprise nitrogen-containing polymer at a level of from about 0.005% to about 1%, preferably from about 0.005% to about 0.3%, and more preferably from about 0.005% to about 0.1%, by weight of the composition.
The nitrogen-containing polymers of the present invention can be comprised of one or more modified polyamines according to the present invention. The modified polyamines of the present invention can be formulated as an admixture wherein a proportional amount of two or more compounds are combined to make up the nitrogen-containing polymers herein.
Alternatively, the formulator can adjust the reaction conditions which form the modified polyamines of the present invention in order to create an admixture of suitable ingredients such as, inter alia, an admixture of polyamine fragments and/or partially crosslinked modified polyamines. Whether a formulated admixture or a product by process is used, or a mixture of both, the compounds which comprise the preferred nitrogen-containing polymers of the present invention generally are selected from the group consisting of:
(a) polyethyleneimine;
(b) polypropyleneimine; and
(c) modified polyamines having the formulae:
(PA)w(T)x;xe2x80x83xe2x80x83(i)
xe2x80x83(PA)w(L)z;xe2x80x83xe2x80x83(ii)
or
[(PA)w(T)x]y[L]z;xe2x80x83xe2x80x83(iii)
wherein PA is a grafted or non-grafted, modified or unmodified polyamine backbone unit, T is an amide-forming polycarboxylic acid crosslinking unit, and L is a non-amide forming crosslinking unit. For compounds of type (i) and (iii) the relative amounts of PA units and T units which are present are such that the molar ratio of PA units to T units is from 0.8:1 to 1.5:1. For compounds of type (ii) the relative amounts of PA units and L units which are present are such that the (PA)w(L)z comprises from about 0.05, preferably from about 0.3 to 2 parts by weight of said L units. Therefore, 1 part of a grafted or non-grafted, modified or unmodified polyamine backbone unit may be combined with from about 0.05, preferably from about 0.3 parts by weight of an L unit to about 2 parts by weight of an L unit to form a suitable modified polyamine compound. Likewise, for compounds of type (iii), crosslinked polyamines having the formula (PA)w(T)x may be combined with from about 0.05, preferably from about 0.3 parts by weight of an L unit to about 2 parts by weight of an L unit to form a suitable modified polyamine compound having the formula [(PA)w(T)x]y[L]z.
Polyamine Backbone (PA Units)
The modified polyamine compounds of the present invention comprise a Polyamine Backbone, PA unit, which can be optionally, but preferably grafted. The following are non-limiting examples of suitable PA units according to the present invention.
Polyalkyleneimine
A preferred PA unit according to the present invention are polyalkyleneimines and polyalkyleneamines having the general formula: 
wherein R is C2-C12 linear alkylene, C3-C12 branched alkylene, and mixtures thereof preferably R is ethylene, 1,3-propylene, and 1,6-hexylene, more preferred is ethylene; B representing a continuation of the chain structure by branching. The indices w, x, and y are such that the molecular weight of said polyamines is from about 50,000 Daltons to about 15,000,000 Daltons, more preferably from about 350,000 Daltons to about 15,000,000 Daltons, even more preferably still from about 600,000 Daltons to about 15,000,000 Daltons. The index w typically has the value of y+1. PA units may be used as crude products or mixtures, and if desired by the formulator, these PA units may be used in the presence of small amounts of diamines as described herein above, wherein the amount of diamines, inter alia, ethylene diamine, hexamethylene diamine may be present up to about 10% by weight, of the PA unit mixture.
Co-polymeric Polyamines
Another example of a preferred PA unit according to the present invention are the polyvinyl amine homo-polymers or co-polymers having the formula: 
wherein V is a co-monomer, non-limiting examples of which include vinyl amides, vinyl pyrrolidone, vinyl imidazole, vinyl esters, vinyl alcohols, and mixtures thereof, all of which can be taken together or in combination with polyvinyl amine to form suitable co-polymerization products suitable for use in the soil entrainment system of the present invention.
The indices w, x, y, m(when present), and n, when present, are such that the molecular weight of said polyamines is from about 50,000 Daltons to about 15,000,000 Daltons, more preferably from about 350,000 Daltons to about 15,000,000 Daltons, even more preferably still from about 600,000 Daltons to about 15,000,000 Daltons.
Polyamine Backbone Modifications
Optionally, but preferably, the PA units of the present invention are modified either before or after reaction with a T unit or L unit crosslinking agent. The two preferred types of modifications are grafting and capping.
Preferably the PA units of the present invention are grafted, that is the PA unit is further reacted with a reagent which elongates said PA unit chain, preferably by reaction of the nitrogens of the PA backbone unit with one or more equivalents of aziridine (ethyleneimine), caprolactam, and mixtures thereof. Grafting units, in contrast to the xe2x80x9ccappingxe2x80x9d units described herein below, can further react on themselves to provide PA unit chain propagation. An example of a preferred grafted PA unit of the present invention has the formula: 
wherein R, B, w, x, and y are the same as defined herein above and G is hydrogen or an extension of the PA unit backbone by grafting. Non-limiting examples of preferred grafting agents are aziridine (ethyleneimine), caprolactam, and mixtures thereof. A preferred grafting agent is aziridine wherein the backbone is extended by units having the formula: 
wherein Bxe2x80x2 is a continuation by branching wherein the graft does not exceed about 12 units, preferably xe2x80x94CH2CH2NH2 and the value of the indices p+q have the value from 0, preferably from about 1, more preferably from about 2 to about 7, preferably to about 5. Another preferred grafting unit is caprolactam.
The PA units of the present invention can be grafted prior to or after crosslinking with one or more T units described herein below, preferably the grafting is accomplished after crosslinking with said T unit. This allows the formulator to take advantage of the differential reactivity between the primary and secondary amino units of the PA unit backbone thereby allowing the formulator to controllably link said PA units and to also control the amount of subsequent branching which results from the grafting step.
Another optional but preferred PA unit modification is the presence of xe2x80x9ccappingxe2x80x9d units. For example, a PA unit is reacted with an amount of a monocarboxylic acid, non-limiting examples of which are C1-C22 linear or branched alkyl, preferably C10-C18 linear alkyl, inter alia, lauric acid, myristic acid. The amount of capping unit which is reacted with the PA unit is an amount which is sufficient to achieve the desired properties of the formula. However, the amount of capping unit used is not sufficient to abate any further crosslinking or grafting which the formulator may choose to perform.
Crosslinking Units
Amide-forming T Crosslinking Units
T crosslinking units are preferably carbonyl comprising polyamido forming units. The T units are taken together with PA units to form crosslinked modified polyamine compounds having the formula (PA)w(T)x or [(PA)w(T)x]y[L]z.
A preferred embodiment of the present invention includes crosslinked PA units wherein a T unit provides crosslinking between two or more PA units to form a (PA)w(T)x polyamido crosslinked section. A preferred crosslinking T unit has the general formula: 
wherein R1 is methylene, phenylene, and mixtures thereof; preferably methylene. The index k has the value from 2 to about 8, preferably to about 4. Preferred values of k are 2, 3, and 4. R2 is xe2x80x94NHxe2x80x94 thereby forming a urethane amide linkage when said R2 comprising T units react with the backbone nitrogens of the PA units. The value of the index j is independently 0 or 1. The presence of R2 units can result, for example, from the use of diisocyanates as crosslinking agents. Non-limiting examples of dibasic acids which are used as a source for T units in the above formula include succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid, and terephthalic acid. However, the formulator is not limited to crosslinking T units deriving from dibasic acids, for example, tribasic crosslinking T units, inter alia, citrate, may be used to link the PA units of the present invention.
Examples of (PA)w(T)x compounds according to the present invention are obtained by condensation of dicarboxylic acids, inter alia, succinic acid, maleic acid, adipic acid, terephthalic acid, with polyalkylene polyamines, inter alia, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine wherein the ratio of the dicarboxylic acid to polyalkyleneamine is from 1:0.8 to 1:1.5 moles, preferably a ratio of from 1:0.9 to 1:1.2 moles wherein the resulting crosslinked material has a viscosity in a 50% by weight, aqueous solution of more than 100 centipoise at 25xc2x0 C.
Non-amide Forming L Crosslinking Units
Another preferred embodiment of the polyamines of the present invention are (PA)w(T)x units which are further crosslinked by L units to form polyamido amines having the formula [(PA)w(T)x]y[L]z or are reacted with PA units to form non-amide polyamines having the formula (PA)w(L)z.
The L units of the present invention are any unit which suitably crosslinks PA units or (PA)w(T)x units. Preferred L linking units comprise units which are derived from the use of epihalohydrins, preferably epichlorohydrin, as a crosslinking agent. The epihalohydrins can be used directly with the PA units or suitably combined with other crosslinking adjuncts non-limiting examples of which include alkyleneglycols, and polyalkylene polyglycols, inter alia, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol-1,6-glycerol, oligoglycerol, pentaerythrites, polyols which are obtained by the reduction of carbohydrates (sorbitol, mannitol), monosaccharides, disaccharides, oligosaccharides, polysaccharides, polyvinyl alcohols, and mixtures thereof.
For example, a suitable L unit is a dodecylene unit having the formula:
xe2x80x94(CH2)12xe2x80x94
wherein an equivalent of 1,12-dichlorododecane is reacted, for example, with a suitable amount of a PA unit to produce a polyamine which is crosslinked via dodecylene units. For the purposes of the present invention, L crosslinking units which comprise only carbon and hydrogen are considered to be xe2x80x9chydrocarbylxe2x80x9d L units. Preferred hydrocarbyl units are polyalkylene units have the formula:
xe2x80x94(CH2)nxe2x80x94
wherein n is from 1 to about 50.
Hydrocarbyl L units may be derived from hydrocarbons having two units which are capable of reacting with the nitrogen of the PA units. Non-limiting examples of precursors which result in the formation of hydrocarbyl L units include 1,6-dibromohexane, 1,8-ditosyloctane, and 1,4-dichlorotetradecane.
Further examples of preferred non-amide forming crosslinking L units are the units which derive from crosslinking units wherein epihalohydrin is used as the connecting unit. For example, 1,12-dihydroxydodecane is reacted with epichlorohydrin to form the bis-epoxide non-amide forming L unit precursor having the formula: 
which when reacted with one or more PA units or (PA)w(T)x units results in an L crosslinking unit having the formula: 
however, it is not necessary to pre-form and isolate the bis-epoxide, instead the crosslinking unit precursor may be formed in situ by reaction of 1,12-dihydroxydodecane or other suitable precursor unit with epihalohydrin in the presence of grafted or ungrafted PA units or (PA)w(T)x units.
Other crosslinking L units which utilize one or more epihalohydrin connecting units include polyalkyleneoxy L units having the formula: 
wherein R1 is ethylene, R2 is 1,2-propylene, x is from 0 to 100 and y is from 0 to 100.
Another preferred unit which can comprise an L unit and which can be suitably combined with epihalohydrin connecting units include polyhydroxy units having the formula: 
wherein the index t is from at least 2 to about 20 and the index u is from 1 to about 6. The formulator may also combine units to form hybrid L crosslinking units, for example, units having the formula: 
wherein the indices w and y are each independently from 1 to 50, z is units are present in a sufficient to suitably connect the polyhydroxy units and the polyalkyleneoxy units into the backbone without the formation of ether linkages.
The following is an example of an L linking group which comprises both a polyalkyleneoxy and a polyhydroxy unit: 
A further example of a preferred crosslinking L units are units which comprises at least two aziridine groups as connecting groups, for example an L unit having the formula: 
which can be used to link two (PA)w units, two (PA)w(T)x units, or mixtures thereof.
The polyamines of the present invention may have varying final compositions, for example, (PA)w(T)x, [(PA)w(T)x]y[L]z, [(PA)]w[L]z, and mixtures thereof, wherein each PA unit may be grafted or ungrafted. The indices w and x have values such that the ratio of w to x is from 0.8:1 to 1.5:1; y and z have values such that said polyamido compound comprises from about 0.05, preferably to about 0.3 to 2 parts by weight of said L unit. In the cases wherein no crosslinking takes place the indices w and y will be equal to 1 and x and z will be equal to 0. In the case wherein no crosslinking occurs using L units, the index y is equal to 1 and z is equal to 0. In the case wherein no crosslinking occurs using T units, the indices w and y are equal to 1 and x is equal to 0.
A preferred embodiment of the present invention which comprises PA units, T units, and L units includes the reaction product of:
a) 1 part by weight, of a polyamine obtained by condensation of 1 mole of a dicarboxylic acid with a polyalkylene polyamine (i.e., diethylenetriamine) to the extent wherein at least about 10% of the xe2x80x94NH backbone hydrogens are unmodified by reaction with said dicarboxylic acid, then optionally reacting the obtained polyamine condensation product with up to 12 ethyleneimine units (i.e., grafting of the backbone using aziridine) per basic nitrogen atom; and
b) further reacting the product obtained in (a) with from 0.05, preferably from about 0.3 to about 2 parts by weight, of an L units, inter alia, the reaction product of a polyalkylene oxide having from 8 to 100 alkylene oxide units with epichlorohydrin at a temperature of from about 20xc2x0 C. to about 100xc2x0 C.
Another preferred embodiment of the nitrogen-containing polymers useful in the present invention includes the reaction product of:
a) 1 part by weight, of a polyamidoamine obtained by condensation of 1 mole of a dicarboxylic acid with from about 0.8 to about 1.5 moles of a polyalkylene polyamine then optionally reacting the obtained polyamidoamine condensation product with up to 8 ethyleneimine units per basic nitrogen atom; and
b) further reacting the product obtained in (a) with from about 0.05 to about 2 parts by weight of the reaction product of a polyalkylene oxide having from 8 to 100 alkylene oxide units with epichlorohydrin at a temperature of from about 20xc2x0 C. to about 100xc2x0 C.
A preferred embodiment of the present invention are the water-soluble condensation products which can be obtained by the reaction of:
a) polyalkyleneimines and polyalkyleneimines grafted with ethyleneimines, and mixtures thereof; with
b) at least bifunctional halogen-free cross-linking agents, said agents selected from the group consisting of:
i) ethylene carbonate, propylene carbonate, urea, and mixtures thereof;
ii) mono-carboxylic acids comprising one olefin moiety, inter alia, acrylic acid, methacrylic acid, crotonic acid; and the esters, amides, and anhydrides thereof; polycarboxylic acids, inter alia, oxalic acid, succinic acid, tartaric acid, itaconic acid, maleic acid; and the esters, amides, and anhydrides thereof;
iii) reaction products of polyetherdiamines, alkylenediamines, polyalkylene-diamines, and mixtures thereof, with mono-carboxylic acids comprising one olefin moiety wherein the resulting polyamine comprises a functional units which is selected from the group consisting of at least two ethylenically unsaturated double bonds, carbonamide, carboxyl group, ester group, and mixtures thereof;
iv) at least two aziridine group-containing reaction products of dicarboxylic acid esters with ethyleneimine and mixtures of the cross-linking agents.
However, prior to reaction of (PA)w(T)x units formed herein above, the (PA)w(T)x polyamine compound may be partially amidated (xe2x80x9ccappedxe2x80x9d as described herein above) by treatment with a mono carboxylic acid or the esters of mono carboxylic acids. The formulator may vary the degree to which the backbone nitrogens are amidated according to the desired properties of the final soil entrainment system. Non-limiting examples of suitable mono-carboxylic acids include formic acid, acetic acid, propionic acid, benzoic acid, salicylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, behenic acid, and mixtures thereof.
The high molecular weight modified polyamine condensation products of the present invention (also referred to herein as xe2x80x9cresinsxe2x80x9d) are preferably formed from the reaction of one or more grafted, cross-linked polyethyleneimines and one or more polyethylene and/or polypropylene glycol copolymers, wherein the resulting crosslinked modified polyamines (resins) have a final viscosity of more than or equal to 300 mPa-sec., preferably from 400 to 2,500 mPa-sec. when measured at 20xc2x0 C. in a 20% aqueous solution. The modified polyamine compounds of the present invention are suitably described in U.S. Pat. No. 3,642,572 Eadres et al., issued Feb. 15, 1972, U.S. Pat. No. 4,144,123 Scharf et al., issued Mar. 13, 1979 and U.S. Pat. No. 4,371,674 Hertel et al., issued Feb. 1, 1983, NE 6,612,293, DT 1,946,471, DT 36386, DT 733,973, DE 1,771,814, all of which are incorporated herein by reference. Examples of preferred modified polyamines useful as nitrogen-containing polymers herein are branched polyethyleneimines with a molecular weight of about 25,000 Daltons, and Lupasol(copyright) SK and Lupasol(copyright) SK(A) available from BASF.
C. SURFACTANTS
Surfactants useful in the present compositions will typically be selected from those which are generally used in hard surface cleaning. The surfactant is preferably selected from the group consisting of anionic, nonionic, zwitterionic, cationic, amphoteric and mixtures thereof.
Cationic surfactants, for purposes of the present invention, do not include compounds described as cationic antimicrobial actives in Section I.A. supra. More preferably, the surfactant is a nonionic surfactant. In preferred embodiments, the present compositions are essentially free of, or free of, anionic surfactant, zwitterionic surfactant, and/or amphoteric surfactant.
The antimicrobial, hard surface cleaning compositions of the present invention contain one or more detergent surfactants. It is preferred that these surfactants are selected from the group consisting of anionic, nonionic, zwitterionic, cationic, amphoteric and mixtures thereof. More preferably the detergent surfactant is uncharged and has a linear or branched structure and is a nonionic detergent surfactant. Preferred anionic and nonionic detergent surfactants have hydrophobic chains containing from about 8 to about 18, preferably from about 8 to about 15, carbon atoms. Examples of suitable anionic surfactants include, but are not limited to, linear alkyl sulfates, alkyl sulfonates, and the like. Examples of suitable nonionic surfactants include alkylethoxylates and the like. Examples of zwitterionic surfactants include betaines and sulfobetaines. Examples of amphoteric surfactants include alkylampho glycinates, and alkyl imino propionate. Further examples of suitable surfactants are described in McCutcheon""s Vol. 1: Emulsifiers and Detergents, North American Ed., McCutheon Division, MC Publishing Co., 1995, which is incorporated herein by reference.
One class of preferred nonionic surfactant is alkyl ethoxylates. The alkyl ethoxylates of the present invention are either linear or branched, and contain from about 8 carbon atoms to about 14 carbon atoms, and from about 4 ethylene oxide units to about 25 ethylene oxide units. Examples of alkyl ethoxylates include Neodol(copyright) 91-6, Neodol 91-8(copyright) supplied by the Shell Corporation (P.O. Box 2463, 1 Shell Plaza, Houston, Tex.), and Alfonic(copyright) 810-60 supplied by Vista Corporation, (900 Threadneedle P.O. Box 19029, Houston, Tex.). More preferred surfactants are the alkyl ethoxylates comprising from about 9 to about 12 carbon atoms, and from about 4 to about 8 ethylene oxide units. These surfactants offer excellent cleaning benefits and work synergistically with the required hydrophilic polymers. A most preferred alkyl ethoxylate is C11EO5, available from the Shell Chemical Company under the trade name Neodol(copyright) 1-5.
Alternative nonionic detergent surfactants for use herein are alkoxylated alcohols generally comprising from about 6 to about 16 carbon atoms in the hydrophobic alkyl chain of the alcohol. Typical alkoxylation groups are propoxy groups or propoxy groups in combination with ethoxy groups. Such compounds are commercially available under the tradename Antarox(copyright) available from Rhodia (CN 7500, Cranberry, N.J.). with a wide variety of chain length and alkoxylation degrees. Block copolymers of ethylene oxide and propylene oxide can also be used and are available from BASF under the trade name Pluronic(copyright). Preferred nonionic detergent surfactants for use herein are according to the formula R(X)nH, were R is an alkyl chain having from about 6 to about 16 carbon atoms, preferably from about 9 to about 16, X is a propoxy, or a mixture of ethoxy and propoxy groups, n is an integer of from about 4 to about 30, preferably from about 5 to about 10. Particularly preferred nonionic surfactants of this class include Nonidet(trademark) SF-3 and Nonidet(trademark) SF-S surfactants. Other non-ionic surfactants that can be used include those derived from natural sources such as sugars and include C8-C16 N-alkyl glucose amide surfactants.
Another type of preferred nonionic surfactant are the alkylpolysaccharides that are disclosed in U.S. Pat. No. 5,776,872, issued Jul. 7, 1998 to Giret et al.; U.S. Pat. No. 5,883,059, issued Mar. 16, 1999 to Furman et al.; U.S. Pat. No. 5,883,062, issued Mar. 16, 1999 to Addison et al.; and U.S. Pat. No. 5,906,973, issued May 25, 1999 to Ouzounis et al.; which are all incorporated by reference herein.
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986, incorporated by reference herein, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 t6 about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group. For acidic or alkaline cleaning compositions/solutions suitable for use in no-rinse methods, the preferred alkyl polysaccharide preferably comprises a broad distribution of chain lengths, as these provide the best combination of wetting, cleaning, and low residue upon drying. This xe2x80x9cbroad distributionxe2x80x9d is defined by at least about 50% of the chainlength mixture comprising from about 10 carbon atoms to about 16 carbon atoms. Preferably, the alkyl group of the alkyl polysaccharide consists of a mixtures of chainlength, preferably from about 6 to about 18 carbon atoms, more preferably from about 8 to about 16 carbon atoms, and hydrophilic group containing from about one to about 1.5 saccharide, preferably glucoside, groups per molecule. This xe2x80x9cbroad chainlength distributionxe2x80x9d is defined by at least about 50% of the chainlength mixture comprising from about 10 carbon atoms to about 16 carbon atoms. A broad mixture of chain lengths, particularly C8-C16, is highly desirable relative to narrower range chain length mixtures, and particularly versus lower (i.e., C8-C10 or C8-C12) chainlength alkyl polyglucoside mixtures. It is also found that the preferred C8-16 alkyl polyglucoside provides much improved perfume solubility versus lower and narrower chainlength alkyl polyglucosides, as well as other preferred surfactants, including the C8-C14 alkyl ethoxylates. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6-positions on the preceding saccharide units. The glycosyl is preferably derived from glucose.
Optionally, and less desirably, there can be a polyalkyleneoxide chain joining the hydrophobic moiety and the polysaccharide moiety. The preferred alkyleneoxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from 8 to 18, preferably from 10 to 16, carbon atoms. Preferably, the alkyl group is a straight-chain saturated alkyl group. The alkyl group can contain up to about 3 hydroxyl groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides and/ or galatoses. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta- and hexaglucosides.
To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-,3-, 4- and/or 6-position, preferably predominantly the 2-position.
In the alkyl polyglycosides, the alkyl moieties can be derived from the usual sources like fats, oils or chemically produced alcohols while their sugar moieties are created from hydrolyzed polysaccharides. Alkyl polyglycosides are the condensation product of fatty alcohol and sugars like glucose with the number of glucose units defining the relative hydrophilicity. As discussed above, the sugar units can additionally be alkoxylated either before or after reaction with the fatty alcohols. Such alkyl polyglycosides are described in detail in WO 86/05199 for example. Technical alkyl polyglycosides are generally not molecularly uniform products, but represent mixtures of alkyl groups and mixtures of monosaccharides and different oligosaccharides. Alkyl polyglycosides (also sometimes referred to as xe2x80x9cAPG""sxe2x80x9d) are preferred for the purposes of the invention since they provide additional improvement in surface appearance relative to other surfactants. The glycoside moieties are preferably glucose moieties. The alkyl substituent is preferably a saturated or unsaturated alkyl moiety containing from about 8 to about 18 carbon atoms, preferably from about 8 to about 10 carbon atoms or a mixture of such alkyl moieties. C8-C16 alkyl polyglucosides are commercially available (e.g., Simusol(copyright) surfactants from Seppic Corporation, 75 Quai d""Orsay, 75321 Paris, Cedex 7, France, and Glucopon(copyright) 425 available from Henkel. However, it has been found that purity of the alkyl polyglucoside can also impact performance, particularly end result for certain applications, including daily shower product technology. In the present invention, the preferred alkyl polyglucosides are those which have been purified enough for use in personal cleansing. Most preferred are xe2x80x9ccosmetic gradexe2x80x9d alkyl polyglucosides, particularly C8 to C16 alkyl polyglucosides, such as Plantaren 2000(copyright), Plantaren 2000 N(copyright), and Plantaren 2000 N UP(copyright), available from Henkel Corporation (Postfach 101100, D 40191 Dusseldorf, Germany).
Suitable anionic surfactants typically comprise a hydrophobic chain containing from about 8 carbon atoms to about 18, preferably from about 8 to about 16, carbon atoms, and typically include a sulfonate or carboxylate hydrophilic head group.
Suitable anionic surfactants include the C8-C18 alkyl sulfonates, C10-C14 linear or branched alkyl benzene sulfonates, C10-14 alkyl sulfates and ethoxysulfates (e.g., Stepanol AM(copyright) from Stepan)., C9-C15 alkyl ethoxy carboxylates (Neodox(copyright) surfactants available from Shell Chemical Corporation),. Suitable commercially available sulfonates are available from Stepan under the tradename Bio-Terge PAS-8(copyright) as well as from the Witco Corporation under the tradename Witconate NAS-8(copyright), and Hostapur SAS(copyright) from Hoechst, Aktiengesellschaft, D-6230 Frankfurt, Germany.
Also suitable for use in the present invention are the fluorinated nonionic surfactants. One particularly suitable fluorinated nonionic surfactant is Fluorad(copyright) F 170 (3M). Fluorad(copyright) F 170 has the formula:
8F17SO2N(C2H5)(CH2CH2O)
Also suitable for use in the present invention are silicone containing surfactants. One example of these types of surfactants is Silwet L7604 available from Union Carbide.
Some of the more preferred commercially available surfactants include Neodol(trademark) 11-5, Nonidet(trademark) SF-3, Nonidet(trademark) SF-5, (all Shell Chemical), C8 sulfonate (Witconate NA-8) C11-18 APG (Henkel), and Fluorad(copyright) F170 (3M).
In general, the antimicrobial, hard surface cleaning compositions of the present invention comprise surfactant, preferably nonionic surfactant, at a level of from about 0.001% to about 15%, preferably from about 0.01% to about 7%, and more preferably from about 0.01% to about 1%, by weight of the composition.
In preferred low-surfactant compositions for use in no-rinse cleaning methods, such compositions typically comprise surfactant, preferably nonionic surfactant, at a level of from about 0.005% to about 0.5%, preferably from about 0.005% to about 0.3%, and more preferably from about 0.005% to about 0.1%, by weight of the composition.
D. OPTIONAL INGREDIENTS
1. Aqueous Carrier
The compositions of the present invention can also comprise an aqueous liquid carrier that comprises water and optionally one or more solvents. The aqueous carrier typically comprises from about 50% to about 100%, preferably from about 60% to about 98%, and more preferably from about 80% to about 96%, by weight of the aqueous carrier, of water and from about 0% to about 50%, preferably from about 0.5% to about 30%, and more preferably from about 1% to about 20%, by weight of the aqueous carrier, of optional solvent.
In general, the antimicrobial, hard surface cleaning compositions of the present invention comprise aqueous carrier at a level of from about 50% to about 99.99%, preferably from about 60% to about 90%, and more preferably from about 90% to about 99.99%, by weight of the composition.
In preferred low-surfactant compositions for use in no-rinse cleaning methods, such compositions typically comprise aqueous carrier at a level of from about 98% to about 99.99%, preferably from about 99% to about 99.99%, and more preferably from about 99.5% to about 99.99%, by weight of the composition.
It is preferred that any water in the composition, such as in premixed or ready to use solutions, is deionized or softened water. However, conventional tap water can be used.
The surfactant provides cleaning and/ or wetting even without a cleaning solvent present. However, the cleaning can normally be further improved by the use of the right solvent. By solvent, it is meant an agent which assists the surfactant to remove soils such as those commonly encountered in the home. The solvent also can participate in the building of viscosity, if needed, and in increasing the stability of the composition.
Such solvents typically have a terminal C3-C6 hydrocarbon attached to from one to three ethylene glycol or propylene glycol moieties to provide the appropriate degree of hydrophobicity and, preferably, surface activity. Examples of commercially available hydrophobic cleaning solvents based on ethylene glycol chemistry include mono-ethylene glycol n-hexyl ether (Hexyl Cellosolve(copyright) available from Union Carbide). Examples of commercially available hydrophobic cleaning solvents based on propylene glycol chemistry include the di-, and tri-propylene glycol derivatives of propyl and butyl alcohol, which are available from Arco Chemical, 3801 West Chester Pike, Newtown Square, Pa. 19073) and Dow Chemical (1691 N. Swede Road, Midland, Mich.) under the trade names Arcosolv(copyright) and Dowanol(copyright).
In the context of the present invention, preferred solvents are selected from the group consisting of mono-propylene glycol mono-propyl ether, di-propylene glycol mono-propyl ether, mono-propylene glycol mono-butyl ether, di-propylene glycol mono-propyl ether, di-propylene glycol mono-butyl ether; tri-propylene glycol mono-butyl ether; ethylene glycol mono-butyl ether; di-ethylene glycol mono-butyl ether, ethylene glycol mono-hexyl ether and di-ethylene glycol mono-hexyl ether, methanol, ethanol, isopropanol, n-butanol, iso-butanol, pentanol, 2-methyl-1-butanol, 2-butanone, methoxymethanol, methoxyethanol, methoxy propanol, ethoxypropanol, propoxypropanol, ethoxybutanol and mixtures thereof. xe2x80x9cButylxe2x80x9d includes both normal butyl, isobutyl and tertiary butyl groups. More prefered solvents include ethanol, propanol, propoxypropanol, mono-propylene glycol and mono-propylene glycol mono-butyl ether. The latter two are available under the tradenames Dowanol DPnP(copyright) and Dowanol DPnB(copyright). Di-propylene glycol mono-t-butyl ether is commercially available from Arco Chemical under the tradename Arcosolv PTB(copyright).
The amount of solvent can vary depending on the amount of other ingredients present in the composition. The solvent is normally helpful in providing good cleaning, such as in floor cleaner applications.
2. Buffer
An optional buffering agent may be an active detergent in its own right, or it may be a low molecular weight, organic or inorganic material that is used in this composition solely for maintaining the desired pH. The buffer can be alkaline, acidic or neutral. Preferred buffering agents for compositions of this invention are nitrogen-containing materials. Some examples are amino acids such as lysine or lower alcohol amines like mono-, di-, and tri-ethanolamine. Other preferred nitrogen-containing buffering agents are Tri(hydroxymethyl)amino methane (HOCH2)3CNH3 (TRIS), 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanol, disodium glutamate, N-methyl diethanolamide, 2-dimethylamino-2-methylpropanol (DMAMP), 1,3-bis(methylamine)-cyclohexane, 1,3-diamino-propanol N,Nxe2x80x2-tetra-methyl-1,3-diamino-2-propanol, N,N-bis(2-hydroxyethyl)glycine (bicine) and N-tris(hydroxymethyl)methyl glycine (tricine). Other suitable buffers include ammonium carbamate, citric acid, acetic acid. Mixtures of any of the above are also acceptable. Useful inorganic buffers/alkalinity sources include ammonia, the alkali metal carbonates and alkali metal phosphates, e.g., sodium carbonate, sodium polyphosphate. For additional buffers see McCutcheon""s EMULSIFIERS AND DETERGENTS, North American Edition, 1997, McCutcheon Division, MC Publishing Company Kirk and WO 95/07971 both of which are incorporated herein by reference.
Preferred buffers include, but are not limited to, ammonia, methanol amine, ethanol amine, 2-amino-2-methyl-1-propanol, 2-dimethylamino-2-methyl-1-propanol, 1,3-bis(methylamine)-cyclohexane, acetic acid, glycolic acid and the like. Most preferred among these are ammonia, 1,3-bis(methylamine)-cyclohexane, 2-dimethylamino-2-methyl-1-propanol and acetic acid.
In one preferred aspect the composition of the present invention wherein to minimize streaking/filming problems, the buffering is provided, at least in part, by volatile materials whose molecular weight is less than about 400 g/mole.
If buffer is desirable for cleaning performance, the present compositions will preferably contain at least about 0%, more preferably at least about 0.001%, even more preferably still, at least about 0.01% by weight of the composition of buffering agent. The composition will also preferably contain no more than about 1%, more preferably no more than about 0.75%, even more preferably, no more than about 0.5% by weight of the composition of buffering agent.
3. Perfume
Perfumes and perfumery ingredients useful in the present compositions and processes comprise a wide variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, esters, and the like. Also included are various natural extracts and essences which can comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, and the like. Finished perfumes can comprise extremely complex mixtures of such ingredients. Finished perfumes typically comprise from about 0.005% to about 2%, by weight, of the antimicrobial, hard surface cleaning compositions herein, and individual perfumery ingredients can comprise from about 0.0001% to about 90% of a finished perfume composition.
When present, the perfume comprises from about 0% to about 0.5%, more preferably from about 0.001% to about 0.1%, even more preferably still 0.005% to about 0.08%, by weight of the composition.
4. Suds Suppressor
The composition of the present invention can optionally contain a suds suppressor. When present the suds suppressor is preferably present from about 0.0005% to about 0.01%, more preferably from about 0.001% to about 0.005%, by weight of the composition.
Suitable suds suppressors include, silicone suds suppressor such as silicone polymers and linear or branched C10-C18 fatty acids or alcohols, with silicone suds suppressor being preferred. One suitable suds supressor is Dow Corning Silicone Suds Supressor.
Another suitable suds suppressors is a mixture of Polyethylene glycol stearate (4% Wt, CAS #9004993); Methylated silica (2% Wt, CAS #67762907); Octamethyl cyclotetrasiloxane (2% Wt, CAS #556672), available from Dow Corning.
Further examples of suitable suds suppressors can be found in co-pending U.S. patent application Ser. No. 09/381,550 filed Sep. 20, 1999 by R. A. Masters et al. (PandG Case 6555), which is incorporated herein by reference.
Other optional ingredients in the present compositions include colorants or dyes, and the like.
In another aspect of the present invention a kit is provided for. This kit can have an assembly of one or more units, either packaged together or separately. For example, the kit can include a pad or a dry wipe with cleaning solution. A second example is a kit with pad or dry wipe, implement and solution. A third example is a kit with concentrated refill, ready to use solution and pads with superabsorbent material. This kit comprises an implement containing a pad containing superabsorbent material and a detergent composition that provides effective cleaning and good particulate soil removal when used with a disposable cleaning pad and without rinsing comprising an effective amount of an soil entrainment system.
It is preferred that the implement comprises:
a. a handle; and
b. a removable cleaning pad preferably containing an effective amount of a superabsorbent material, and having a plurality of substantially planar surfaces, wherein each of the substantially planar surfaces contacts the surface being cleaned, more preferably said pad is a removable cleaning pad having a length and a width, the pad comprising
i. a scrubbing layer; and
ii. an absorbent layer comprising a first layer and a second layer, where the first layer is located between the scrubbing layer and the second layer (i.e., the first layer is below the second layer) and has a smaller width than the second layer.
An important aspect of the cleaning performance provided by the preferred pad is related to the ability to provide multiple planar surfaces that contact the soiled surface during the cleaning operation. In the context of a cleaning implement such as a mop, these planar surfaces are provided such that during the typical cleaning operation (i.e., where the implement is moved back and forth in a direction substantially perpendicular to the pad""s width), each of the planar surfaces contact the surface being cleaned as a result of xe2x80x9crockingxe2x80x9d of the cleaning pad.
In one preferred aspect of the present invention, the kit further contains instructions for use of the kit which are in association with the composition and the implement to insure optimum usage. In a further preferment of this aspect, these instructions are on the back of the pad in the form of words and/or pictures and explain which side of the pad to attach to the implement.
In one preferred aspect of the implement the pad is detachably mounted on the implement. That is, the pad can be removed and replaced by another pad. This is especially useful, when the pad is excessively soiled. The pad can be removed and replaced with a fresh clean pad.
In another preferred aspect the implement further comprises a dosing device. The dosing device delivers the detergent composition to the surface to be cleaned. This dosing device can be battery powered, electrically powered, or hand powered (that is the user works the dosing device, such as a pump manually). It is more preferred that the dosing device be battery or electrically powered and includes a dispensing trigger or button. It is even more preferred that when the dosing device is battery or electrically powered, it applies a continuous flow to the surface to be cleaned.
In another preferred aspect the implement further comprises a reservoir which holds the cleaning solution. It is preferred that, when present, the reservoir is detachably mounted on the implement. It is even more preferred that when implement comprises a detachably mounted reservoir that the implement also comprises a dosing device, even more preferably a battery or electrically powered dosing device.
In one preferred aspect the pad comprises an inner absorbent core with super-absorbent polymer and outer scrub layer made of an apertured form film.